CN103657625A - Preparation method of rutile type boron-doped titania (B-TiO2) microsphere with exposed high energy crystal face {001} - Google Patents
Preparation method of rutile type boron-doped titania (B-TiO2) microsphere with exposed high energy crystal face {001} Download PDFInfo
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Abstract
The invention provides a preparation method of a rutile type boron-doped titania (B-TiO2) microsphere with an exposed high energy crystal face {001} and belongs to the technical field of the preparation of inorganic material. The preparation method comprises the following specific steps: adding titanium boride (TiB) into a hydrochloric acid solution hydrazine containing natrium fluoride (NaF) to obtain a mixed solution, forcefully agitating, then transferring the mixed solution to a reactor with a polytetrafluoroethene lining, keeping the mixed solution at a constant temperature of 200 DEG C for 12-24 hours, naturally cooling the mixed solution to the room temperature so as to obtain a product, filtering the product, respectively washing and settling the product with distilled water and absolute ethyl alcohol for three times, drying the product at a temperature of 60-80 DEG C for 12-24 hours, and finally preparing the B-TiO2 microsphere with the exposed high energy crystal face {001}, of which exposing rate nearly reaches 100 percent. The preparation method is simple in preparation technology and good in repeatability; the prepared B-TiO2 microsphere is controllable and uniform in size and has a diameter of 3-5 micron; the element boron is doped, and is uniform in distribution and controllable in the amount of dopping; in addition, the prepared B-TiO2 microphere has excellent visible light catalytic activity, and is likely to be widely applied in the fields of photolytic water hydrogen preparation, organic contaminant degradation and the like.
Description
Technical field
The present invention relates to a kind of preparation method of titanium dioxide microballoon sphere, { preparation method of 001} rutile-type boron doped titanic oxide microballoon, belongs to inorganic material preparing technical field to be specifically related to a kind of exposure high energy crystal face.
Background technology
Environmental pollution and energy crisis are two hang-ups of puzzlement current world economy development; a large amount of uses of fossil fuel not only cause huge pollution to global environment and ecology; and these energy are non-renewable resources, it is exhausted that the storage content in the whole world estimates that the middle of this century is about to.Therefore, how to solve problem of environmental pollution extremely urgent.Since Honda in 1972 and Fujishima etc. find TiO
2since Single Crystalline Electrodes has certain redox property under the effect of light, scientists has proposed an energy-efficient solution for solving this difficult problem of environmental pollution: utilize sunshine to carry out decomposing organic pollutant.
Traditional semiconductor light-catalyst is mainly inorganic compound, comprises metal oxide, sulfide, nitride, phosphide and compound thereof etc., and the most representative is TiO
2.TiO
2water insoluble, resistance to corrosion is strong, cheap and facilitate the advantages such as processing, biological function, photochemical properties are stable, environmentally safe, becomes a kind of desirable photochemical catalyst.Yet TiO
2band gap be 3.2 eV, only have wavelength just can excite the transition of valence band electronics lower than the ultraviolet light below 380 nm, and solar spectrum medium ultraviolet light less than 5%, and the visible ray that wavelength is 400-750 nm accounts for 45% left and right, this has fundamentally restricted TiO
2the practical application of photochemical catalyst.At present, researcher widens TiO by methods such as doping, compound, the dye sensitization of semiconductor, noble-metal-supported and conjugated polymers are compound
2light absorption band edge, improve photocatalytic activity.Doping is to TiO
2a kind of effective method of modification, not only can promote TiO
2the red shift of light absorption band edge, and can improve its photocatalytic activity.And exposure has the high energy of exposure crystal face, { 001} rutile-type boron doped titanic oxide microballoon is not reported so far.
Aspect the preparation of boron doped titanic oxide, current preparation method is mainly sol-gel process, and the material that the method is used as boron source is mainly boric acid and triethyl borate, and titanium source comprises that Ti-inorganic salt is as TiCl
4with titanium alkoxide, as isopropyl titanate, butyl titanate.Yet the doping of the method B is limited in titanium dioxide lattice, because B ion doping is too much, will separates out from titanium dioxide crystal inside and form B
2o
3.Mechanical-chemical method also has report, although the preparation process of mechanical-chemical method is simple, due to unbalance stress, the degree of scatter of the distribution of the particle diameter of product and doped chemical is bad.The product purity that hydrothermal synthesis method forms is high, and good dispersion, is divided into a step and two one-step hydrothermals.Wei Fengyu etc. directly carry out titanium salt solution, sulfuric acid and boric acid after hydrothermal treatment consists, and precipitation through repeatedly drying and obtain the codoping modified catalyst of boron sulphur after washing at 90 ℃.Zhao Yan use two one-step hydrothermals such as has rather prepared B-TiO
2, by TiO
2solution mixes with boric acid to stir evenly and is placed in polytetrafluoroethylene (PTFE) reactor, at 85 ℃ of hydro-thermal reaction 5 h, and then in 110 ℃ of reaction 20 h, calcining after the colloid obtaining is dry.
The present invention selects titanium boride as raw material, joins the mixed solution of NaF and hydrochloric acid, under thermal and hydric environment, reacts, and a step can make to have and expose high energy crystal face { 001} rutile-type boron doped titanic oxide, preparation technology is simple, reproducible.The B-TiO preparing
2microballoon size is controlled, size is even, and average diameter is about 3-5 μ m; Boron element is bulk phase-doped, is evenly distributed, and doping size is controlled; { 001} exposure almost reaches 100% to high energy crystal face.The B-TiO preparing
2microballoon has excellent visible light catalysis activity, is expected to obtain in fields such as photolysis water hydrogen, degradable organic pollutants application widely.
Summary of the invention
The invention provides a kind of exposure high energy crystal face { 001} rutile-type boron doped titanic oxide (B-TiO
2) preparation method of microballoon, preparation technology is simple, reproducible; The B-TiO preparing
2microballoon size is controlled, size is even, and average diameter is about 3-5 μ m, and { 001} exposure almost reaches 100% to high energy crystal face, and B-TiO
2microballoon has excellent visible light catalysis activity.
For realizing the object of foregoing invention, the technical scheme that the present invention takes is as follows:
A kind of exposure high energy crystal face { 001} rutile-type B-TiO
2the preparation method of microballoon, comprises the steps:
(1) 500 mg ~ 1000 mg titanium borides are joined in the mixed solution of NaF and hydrochloric acid, wherein the concentration of NaF is 0.015mol/L, and the concentration of hydrochloric acid is 1-3 mol/L, and strong stirring 15 ~ 60 min obtain mixed liquor;
(2) mixed liquor step (1) being obtained is transferred in the hydrothermal reaction kettle of liner four polyvinyl fluorides;
(3) hydrothermal reaction kettle of liner four polyvinyl fluorides is placed in to drying box, keeps 200 ℃ of constant temperature, reaction 12 ~ 24 h, then naturally cool to room temperature;
(4) step (3) products therefrom is filtered, with distilled water, absolute ethanol washing, precipitate each three times, then, at 60 ~ 80 ℃, dry 12 ~ 24 h, make B-TiO
2microballoon.
Titanium boride and sodium fluoride described in step (1) are pure for analyzing, and purity is 99%, and hydrochloric acid is the solution after concentrated hydrochloric acid dilution, and concentrated hydrochloric acid concentration is 36.5%.
Described in step (3), keep 200 ℃ of constant temperature, reaction 12 ~ 24 h refer to: under hydrothermal condition, drying box constant temperature is at 200 ℃, and constant temperature time is 12 ~ 24 h.
It is stable that thermostat temperature described in step (3) keeps, and temperature fluctuation range is ± 0.1 ℃.
A kind of exposure high energy crystal face { the 001} rutile-type boron doped titanic oxide (B-TiO that adopts the present invention to prepare
2) microballoon is applied in visible ray effect catalytic degradation organic contamination reaction, for example at normal temperatures, the reaction time is 2.5h, result shows B-TiO prepared by the present invention
2microballoon has excellent catalytic activity.
To the B-TiO that adopts the inventive method to make
2microballoon adopt the D8 ADVANCE type X-ray powder diffraction instrument (XRD) that German Bruker company produces (
λ cu =0.15418 nm) carry out Crystalline form analysis (as Fig. 1), result shows: products therefrom is rutile titanium dioxide; Adopt LEO1530VP type field emission scanning electron microscope (SEM) to carry out morphology analysis (as Fig. 2), result shows: gained titanium dioxide is spherical in shape, and by the active crystal face of much exposure high energy, { 001} nanometer sheet forms, and diameter is about 3-5 μ m; Adopt the photoelectricity power spectrum of Britain VG ESM-LAB to carry out XPS analysis (as Fig. 3) to the material making, result shows to have B, Ti and tri-kinds of elements of O in product, illustrates and exists boron element to be successfully doped in titanium dioxide.
To the B-TiO that adopts the inventive method to make
2microballoon and nitrogen-doped titanium dioxide (N-P25) have carried out the effect comparison (as Fig. 4) of photo-catalytic degradation of methyl-orange under visible ray effect, and result shows, although particle is than N-P25(50nm left and right) large, the B-TiO of preparation
2microballoon shows more high visible catalytic effect.This photochemical catalyst can be in extensive uses such as photolysis water hydrogen, degradable organic pollutants.
the present invention's beneficial effect is compared with prior art:
(1) its technology preparation condition of preparation method of the present invention is gentleer, and equipment is simple.Boron element is bulk phase-doped, is evenly distributed, and doping size is controlled.Without high temperature crystallization, avoided high-temperature process to the pattern of product and stability influence;
(2) under hydrothermal condition, take titanium boride directly obtains rutile-type B-TiO as raw material
2microballoon, prepared B-TiO
2microballoon has advantages of that size is controlled, size evenly, visible light photocatalysis active is high, particularly expose the active crystal face of high energy 001}, exposure almost reaches 100%;
(3) B-TiO that prepared by the present invention
2microballoon is compared with the effect that nitrogen-doped titanium dioxide (N-P25) has carried out photo-catalytic degradation of methyl-orange under visible ray effect, has more high catalytic activity.
Accompanying drawing explanation
Fig. 1 is the B-TiO that the present invention makes
2microballoon X-ray powder diffraction (XRD) figure;
Fig. 2 is the B-TiO that the present invention makes
2microballoon SEM (SEM) figure;
Fig. 3 is the B-TiO that the present invention makes
2microballoon photoelectron spectroscopy (XPS) collection of illustrative plates;
Fig. 4 is the B-TiO that the present invention makes
2microballoon (a) and nitrogen-doped titanium dioxide (N-P25) (b) have carried out the effect comparison diagram of photo-catalytic degradation of methyl-orange under visible ray effect.
The specific embodiment
Below by embodiment, the present invention is described in further details, these embodiment are only used for illustrating the present invention, do not limit the scope of the invention.
embodiment 1
In the beaker of 250 ml, add 500 mg titanium boride (TiB, 99%) in the hydrochloric acid solution that contains 0.015 mol/L sodium fluoride to 70 ml, wherein the concentration of hydrochloric acid is 1.0 mol/L, strong stirring 30 min, then transfer in 100 ml liner four polyvinyl fluoride hydrothermal reaction kettles, put in 200 ℃ of thermostatic drying chambers, under solvent heat condition, keep reaction 24 h.After reaction finishes, naturally cool to room temperature, with distilled water and absolute ethyl alcohol, respectively wash three times, make after product is placed in to 70 ℃ of drying box vacuum drying 12 h.The B-TiO that adopts this step to prepare
2microsphere diameter approximately 3 μ m.
embodiment 2
In the beaker of 250 ml, add 1000 mg titanium boride (TiB, 99%) in the hydrochloric acid solution that contains 0.015 mol/L sodium fluoride to 70 ml, wherein the concentration of hydrochloric acid is 1.5 mol/L, strong stirring 15 min, then transfer in 100 ml liner four polyvinyl fluoride hydrothermal reaction kettles, put in 200 ℃ of thermostatic drying chambers, under solvent heat condition, keep reaction 18 h.After reaction finishes, naturally cool to room temperature, with distilled water and absolute ethyl alcohol, respectively wash three times, make after product is placed in to 80 ℃ of drying box vacuum drying 12 h.The B-TiO that adopts this step to prepare
2microsphere diameter approximately 3.8 μ m.
embodiment 3
In the beaker of 250 ml, add 800 mg titanium boride (TiB, 99%) in the hydrochloric acid solution that contains 0.015 mol/L sodium fluoride to 70 ml, wherein the concentration of hydrochloric acid is 2.0 mol/L, strong stirring 40 min, then transfer in 100 ml liner four polyvinyl fluoride hydrothermal reaction kettles, put in 200 ℃ of thermostatic drying chambers, under solvent heat condition, keep reaction 20 h.After reaction finishes, naturally cool to room temperature, with distilled water and absolute ethyl alcohol, respectively wash three times, make after product is placed in to 75 ℃ of drying box vacuum drying 18 h.The B-TiO that adopts this step to prepare
2microsphere diameter approximately 4.2 μ m.
embodiment 4
In the beaker of 250 ml, add 600 mg titanium boride (TiB, 99%) in the hydrochloric acid solution that contains 0.015 mol/L sodium fluoride to 70 ml, wherein the concentration of hydrochloric acid is 2.5 mol/L, strong stirring 50 min, then transfer in 100 ml liner four polyvinyl fluoride hydrothermal reaction kettles, put in 200 ℃ of thermostatic drying chambers, under solvent heat condition, keep reaction 12h.After reaction finishes, naturally cool to room temperature, with distilled water and absolute ethyl alcohol, respectively wash three times, make after product is placed in to 70 ℃ of drying box vacuum drying 22 h.The B-TiO that adopts this step to prepare
2microsphere diameter approximately 4.8 μ m.
embodiment 5
In the beaker of 250 ml, add 700 mg titanium boride (TiB, 99%) in the hydrochloric acid solution that contains 0.015 mol/L sodium fluoride to 70 ml, wherein the concentration of hydrochloric acid is 3.0 mol/L, strong stirring 60 min, then transfer in 100 ml liner four polyvinyl fluoride hydrothermal reaction kettles, put in 200 ℃ of thermostatic drying chambers, under solvent heat condition, keep reaction 15 h.After reaction finishes, naturally cool to room temperature, with distilled water and absolute ethyl alcohol, respectively wash three times, make after product is placed in to 80 ℃ of drying box vacuum drying 24 h.The B-TiO that adopts this step to prepare
2microsphere diameter approximately 5 μ.
Claims (4)
1. one kind exposes high energy crystal face { 001} rutile-type B-TiO
2the preparation method of microballoon, is characterized in that: comprise the steps:
(1) 500 mg ~ 1000 mg titanium borides are joined in the mixed solution of NaF and hydrochloric acid, wherein the concentration of NaF is 0.015mol/L, and the concentration of hydrochloric acid is 1.0-3.0 mol/L, and strong stirring 15 ~ 60 min obtain mixed liquor;
(2) mixed liquor step (1) being obtained is transferred in the hydrothermal reaction kettle of liner four polyvinyl fluorides;
(3) hydrothermal reaction kettle of liner four polyvinyl fluorides is placed in to drying box, keeps 200 ℃ of constant temperature, reaction 12 ~ 24 h, then naturally cool to room temperature;
(4) step (3) products therefrom is filtered, with distilled water, absolute ethanol washing, precipitate each three times, then, at 60 ~ 80 ℃, dry 12 ~ 24 h, make B-TiO
2microballoon.
2. a kind of exposure high energy crystal face { 001} rutile-type B-TiO according to claim 1
2the preparation method of microballoon, is characterized in that: titanium boride and sodium fluoride described in step (1) are pure for analyzing, and purity is 99%; Hydrochloric acid is the solution of concentrated hydrochloric acid dilution, and concentrated hydrochloric acid volumetric concentration is 36.5%.
3. a kind of exposure high energy crystal face { 001} rutile-type B-TiO according to claim 1
2the preparation method of microballoon, is characterized in that: described in step (3), keep 200 ℃ of constant temperature, reaction 12 ~ 24 h refer to: under hydrothermal condition, drying box constant temperature is at 200 ℃, and constant temperature time is 12 ~ 24 h.
4. according to a kind of exposure high energy crystal face { the 001} rutile-type B-TiO described in claim 1 or 3
2the preparation method of microballoon, is characterized in that: thermostat temperature described in step (3) keeps stable, and temperature fluctuation range is ± 0.1 ℃.
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Cited By (6)
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|---|---|---|---|---|
| CN104310468A (en) * | 2014-10-14 | 2015-01-28 | 吉林大学 | Method for preparing monodisperse titanium dioxide (B) nano particles |
| CN104607165A (en) * | 2015-02-10 | 2015-05-13 | 哈尔滨工业大学 | Preparation method of photocatalyst containing boron cross-shaped titanium dioxide |
| CN107999050A (en) * | 2017-11-28 | 2018-05-08 | 阜阳师范学院 | A kind of B-TiO2The preparation and its application of photochemical catalyst |
| CN108543528A (en) * | 2018-04-10 | 2018-09-18 | 陕西科技大学 | It is a kind of to prepare different-shape rutile TiO2The method of photochemical catalyst |
| CN108598455A (en) * | 2018-04-26 | 2018-09-28 | 福州大学 | Graded structure TiO2The preparation method of-B and its application in lithium ion battery |
| CN113087011A (en) * | 2021-03-31 | 2021-07-09 | 福州大学 | Titanium dioxide B-phase material and preparation method and application thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104310468A (en) * | 2014-10-14 | 2015-01-28 | 吉林大学 | Method for preparing monodisperse titanium dioxide (B) nano particles |
| CN104310468B (en) * | 2014-10-14 | 2016-01-27 | 吉林大学 | One prepares the method for monodisperse titanium dioxide (B) nanoparticle |
| CN104607165A (en) * | 2015-02-10 | 2015-05-13 | 哈尔滨工业大学 | Preparation method of photocatalyst containing boron cross-shaped titanium dioxide |
| CN107999050A (en) * | 2017-11-28 | 2018-05-08 | 阜阳师范学院 | A kind of B-TiO2The preparation and its application of photochemical catalyst |
| CN108543528A (en) * | 2018-04-10 | 2018-09-18 | 陕西科技大学 | It is a kind of to prepare different-shape rutile TiO2The method of photochemical catalyst |
| CN108598455A (en) * | 2018-04-26 | 2018-09-28 | 福州大学 | Graded structure TiO2The preparation method of-B and its application in lithium ion battery |
| CN108598455B (en) * | 2018-04-26 | 2020-08-11 | 福州大学 | Hierarchical structure TiO2Preparation method of (E) -B and application thereof in lithium ion battery |
| CN113087011A (en) * | 2021-03-31 | 2021-07-09 | 福州大学 | Titanium dioxide B-phase material and preparation method and application thereof |
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